Divergent Oxidative Rearrangements in Solution and in a Zeolite: Distal vs Proximal Bond Cleavage of Methylenecyclopropanes
作者:Hiroshi Ikeda、Tsuyoshi Nomura、Kimio Akiyama、Mitsuhiro Oshima、Heinz D. Roth、Shozo Tero-Kubota、Tsutomu Miyashi
DOI:10.1021/ja045930n
日期:2005.10.1
2-dihydronaphthalene (9) were isolated from the supernatant solution. The sharp contrast between the photoinduced electron-transfer reaction with photosensitizers in solution and the spontaneous reaction with redox-active acidic zeolite offers the prospect of further zeolite-induced regiodivergent reactions in a range of additional substrates.
在 CH(2)Cl(2) 中存在 E-1-benzylidene-2-phenylcyclopropane (E-5) 的情况下照射 9,10-二氰基蒽 (DCA) 或对氯苯醌会导致 E-5 发生亚甲基环丙烷重排。DCA 和 5 之间的加合物 Z-7 坚定地支持双功能三亚甲基甲烷自由基阳离子的参与。相比之下,将 E-5 掺入 HZSM-5 会产生反式,反式-1,4-二苯基-1,3-丁二烯自由基阳离子,螯合在 HZSM-5 内部,tt-8(.+)@HZSM-5,通过 ESR 和漫反射光谱识别。此外,从上清液中分离出低产率的 tt-8、其顺式、反式异构体 (ct-8) 和 1-苯基-1,2-二氢萘 (9)。